This invention is directed to composites using, as the matrix resin, novel aryl ether sulphone polymers containing the following ether-linked units: ##STR1## and two or more of the following: ##STR2## wherein R is selected from SO.sub.2, SO, O, CO, C.sub.1 -C.sub.4 alkylidene and a direct bond.
A select class of polyaryl ether sulphones containing a unit derived from 4,4-bis(-p-halophenylsulfonyl)diphenyl is described in the art. U. S. Pat. No. 3,647,751 depicts polymers of the following formula: ##STR3## wherein Ar is defined as a diphenylene or nahthylene radical or a polynuclear divalent radical of formula: ##STR4## wherein Z is a divalent aliphatic, cycloaliphatic or araliphatic radical containing 1-8 carbon atoms or --O--, --S--, --SO--, --SO.sub.2 -- or --CO--. Example 3 of U.S. Pat. No. 3,647,751, the only example of a polymer derived from a 4,4-bis-p-halobenzenesulfonyl)biphenyl, depicts the following structure: ##STR5##
U.S. Pat. No. 3,643,355 describes a number of polymers prepared from 4,4'-bis(4-chlorophenylsulphonyl)biphenyl. In Example 5 the following polymer is provided: ##STR6## In example 16 the following polymer is depicted: ##STR7## In example 17 the same structure is shown except that both units (I) and (II) are present in amounts of 50 mole precent.
U.S. Pat. No. 4,009,149 describes, as the sole polymer therein, an aromatic polysulphone consisting of repeating units having the formula: ##STR8##
The polymer is described as amorphous and having a glass transition temperature (Tg) of about 260.degree. C. However, applicants have prepared this polymer (See Control B in Table I) and found it to be slightly crystalline and not amorphous.
British Patent Specification No. 1,295,584, in Table 1, describes a polymer produced from hydroquinone and 4,4'-bis(4-chlorophenylsulphonyl)biphenyl. This polymer is structurally the same as the polymer of U.S. Pat. No. 4,009,149 depicted above. However, the polymer is described in the British Specification as crystalline in that it has a crystalline melting point of 350.degree. C. Also described in Table 1 of the British Specification are polymers prepared from dithiohydroquinone and 4,4'-bis(4-chlorophenylsulphonyl)biphenyl and from monothiohydroquinone and 4,4'-bis(4-chlorophenyl-sulphonyl)biphenyl. The latter polymer is described as amorphous. Example 4 of the British Specification describes the preparation of a polymer from monothiohydroquinone, 4,4'-dichlorodiphenylsulphone and 4,4'-bis(4-chlorophenyl-sulphonyl)biphenyl.
U.S. Pat. No. 4,008,203 broadly discloses a host of polysulphones. Although this patent does not specifically disclose or describe polymers derived from 4,4-bis(halophenysulfonyl)biphenyl, the repeat unit defined broadly therein might be construed by some as having a unit that could be derived from 4,4-bis(halophenylsulfonyl)biphenyl.
The polymers of the prior art produced from hydroquinone and 4,4-bis(4-chlorophenylsulphonyl)biphenyl as described in U.S. Pat. No. 4,009,149 and British Patent Specification No. 1,295,584 are deficient in that they do not readily dissolve in common solvents such as N-methylpyrrolidinone and therefore cannot be cast into film. The polymers produced from 4,4'-bis(4-chlorophenylsulphonyl)biphenyl and biphenol as described in U.S. Pat. No. 3,647,751 are crystalline polymers having a Tg of 270.degree. C. They do not readily dissolve in common solvents such as N-methylpyrrolidione and are difficult to cast into film or spin into hollow fibers.
Many of the prior art resins based on 4,4-bis(4-chlorophenylsulfonyl)biphenyl tend to be rigid and somewhat brittle, particularly when crystalline. In addition, the presence of a high crystalline melt temperature for some of these materials hinders thermal processing and may limit their use, particularly in the production of thermoformable goods and laminates.
Heat resistant, amorphous thermoplastic resins with good toughness that are more readily processable both thermally and from solution would be a useful advance in the art. Such thermoplastics would be particularly useful in the production of laminates and fiber-reinforced composites where good thermoforming characteristics, a useful degree of solubility sufficient to permit impregnating and coating operations, and good film-forming properties are particularly important.